1. Field of the Invention
This invention relates to a process for the selective production of para-substituted benzenes by catalytic alkylation of toluene or ethylbenzene in the presence of a specified crystalline aluminosilicate zeolite catalyst.
2. Description of the Prior Art
Alkylation or aromatic hydrocarbons utilizing crystalline aluminosilicate catalysts has heretofore been described. U.S. Pat. No. 2,904,697 to Mattox refers to alkylation of aromatic hydrocarbons with an olefin in the presence of a crystalline metallic aluminosilicate having uniform pore openings of about 6 to 15 Angstrom units. U.S. Pat. No. 3,251,897 to Wise describes alkylation of aromatic hydrocarbons in the presence of X- or Y-type crystalline aluminosilicate zeolites, specifically such type zeolites wherein the cation is rare earth and/or hydrogen. U.S. Pat. No. 3,751,504 to Keown et al. and 3,751,506 to Burress describe vapor phase alkylation of aromatic hydrocarbons with olefins, e.g. benzene with ethylene, in the presence of a ZSM-5 type zeolite catalyst.
The alkylation of toluene with methanol in the presence of a cation exchanged zeolite Y has been described by Yashima et al. in the Journal of Catalysis 16, 273-280 (1970). These workers reported selective production of para-xylene over the approximate temperature range of 200.degree. to 275.degree. C., with the maximum yield of para-xylene in the mixture of xylenes, i.e. about 50 percent of the xylene product mixture, being observed at 225.degree. C. Higher temperatures were reported to result in an increase in the yield of meta-xylene and a decrease in production of para and ortho-xylenes.
While the above-noted prior art is considered of interest in connection with the subject matter of the present invention, the alkylation process described herein carried out in the presence of a crystalline aluminosilicate zeolite which, in unmodified form, has been found to achieve unexpectedly high selective production of para-substituted benzenes has not, insofar as is known, been heretofore described.
Of the xylene isomers, i.e. ortho-, meta- and para-xylene, the latter is of particular value being useful in the manufacture of terephthalic acid which is an intermediate in the manufacture of synthetic fibers such as "Dacron". Mixtures of xylene isomers either alone or in further admixture with ethylbenzene, generally containing a concentration of about 24 weight percent para-xylene in the equilibrium mixture, have been previously separated by expensive superfraction and multistage refrigeration steps. Such process, as will be realized, has involved high operation costs and has a limited yield.
Both ethyltoluene and diethylbenzene are valuable chemicals. They may be dehydrogenated to produce the corresponding vinyltoluene and divinylbenzene. It has heretofore been recognized that the presence of substantial quantities of the ortho isomers are highly undesirable in the charge undergoing dehydrogenation since they tend to lead to ring closure with formation of the corresponding indenes and indanes from ortho-ethyltoluene and naphthalene or its derivatives from ortho-diethylbenzene, which adversely affect the properties of the resultant polymer. The indenes, indanes and naphthalenes so formed are difficult to separate from the desired vinyl aromatic products. It has accordingly heretofore been necessary to remove the ortho isomers from the ethyltoluene and diethylbenzene charge stocks by expensive distillation techniques prior to dehydrogenation thereof.
It is evident that the availability of ethyltoluene or diethylbenzene in which the ortho isomer is initially absent or present only in trace amount would eliminate the necessity for expensive prior removal of this isomer. Such products have, however, not heretofore been available.